JPH03276166A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To make a toner fit for full-color development and to stabilize electrostatic charging at low temp. and humidity or high temp. and humidity and at the time of repeated use by adding a colorless electrostatic charge control agent contg. silicon. CONSTITUTION:this toner contains a complex compd. contg. silicon obtd. by coordinating mono- or polycyclic arom. diol, mono- or polycyclic arom. hydroxycarboxylic acid, mono- or polycyclic arom. dicarboxylic acid capable of forming a chelate by >=2 mol per 1 mol silicon. The complex compd. is a colorless compd. acting as a negative charge control agent and a concrete example is a compd. represented by the formula (a counter ion may be a proton or a cation such as an alkali metal ion).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a toner used for electrostatic image development in electrophotography, electrostatic recording, and the like.

(Prior Art) Conventionally, various charge control agents have been used to control the charge of toner, but negative charge control agents include chromium lead salts of azo dyes and aromatic hydroxycarboxylic acids. Colored ones such as chromium complex salts are known, and aluminum, zinc, or boron complex salts of aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids are known as colorless negative charge control agents.

(Problem to be Solved by the Invention) The former colored toner has a remarkable effect of imparting a negative charge to the toner, but because it is colored, it is not suitable for color toners, especially full-color toners for creating full-color images using three primary colors. They had the disadvantage that they could not be used, or even if they were used, only very low-quality reproduced colors could be obtained.

In addition, the latter colorless type does not have a sufficient effect of imparting a negative charge to the toner, and has the drawback of lacking environmental stability of toner charge, and especially lack of long-term chargeability stability during repeated use. Ta.

Furthermore, since many metals including chromium and zinc can be sources of heavy metal contamination, there has been a social demand that their use should be avoided from the standpoint of environmental protection.

The present invention has been made in view of the above-mentioned problems with conventional charge control agents.

That is, an object of the present invention is to provide a color toner, particularly a toner containing a colorless charge control agent for full color toners that can be used in process color copying machines and printers. Another object of the present invention is to provide a toner containing a charge control agent that imparts environmental stability to toner chargeability and charge stability during repeated use. Still another object of the present invention is to provide a toner containing a charge control agent that does not become a source of heavy metal contamination.

(Means for Solving the Problems) The toner of the present invention contains a silicon atom as an essential component, and contains a monocyclic or polycyclic aromatic diol capable of forming a chelate in an amount of 2 moles or more per mole of silicon; Alternatively, it is characterized by containing a complex compound coordinated with a polycyclic aromatic hydroxyl carboxylic acid or a monocyclic or polycyclic aromatic dicarboxylic acid (hereinafter, these are referred to as "silicon-containing complex compounds").

The present invention will be explained in detail below.

In the silicon-containing complex compound described above, which is contained as an essential component in the toner of the present invention, a chelate-formable monocyclic or polycyclic aromatic diol, a monocyclic or polycyclic aromatic hydroxycarboxylic acid, and a monocyclic or polycyclic aromatic Specific examples of group dicarboxylic acids include catechol (1,2 phenyldiol), 2,3-naphthalenediol, 2,2'-
Biphenyldiol, salicylic acid, 2-hydroxy 3-
Sinapthoic acid, orthophthalic acid, 2,3-naphthalene dicarboxylic acid and derivatives thereof, such as alkylated products, alkenylated products, arylated products, alkoxylated products, etc., known chelate-formable aromatic diols, aromatic hydroxycarboxylic acids, and Examples include aromatic dicarboxylic acids.

Examples of the silicon atom-containing complex compounds that can be used in the present invention include those represented by the following general formulas (I) to (IV).

Specific examples thereof include the following.

(A) Exemplary compound group A (4-coordinated S1 compound) (1) Bis(catecholate) silicon (2) Bis(salicylate) silicon (wherein, Ar is O which may be substituted with an alkyl group)
-phenylene group 1.2,3-naphthylene group, 2(I3)
Exemplary compound group B (5-coordinated S1 compounds) (3) represents a bis(catecholate)phenyl silicon anion, R represents an alkyl group, an alkoxy group, or an aryl group, and A represents a monovalent or divalent cation. ) (4) Bis(3,5-ditert-butyl-tecorate)
Phenyl silicon anion (8) bis(1,10-biphenyldiorad) phenylke (5) bis (salicylate) phenyl silicon anion (
C) Exemplary compound group C (6-coordinated Si compounds) (9) Tris(catecholate) silicon anion (6) Bis(salicylate) methyl silicon anion (7) Bis(2,8-naphthalene diolado) phenyl silicon anion (10 ) ) Lis(salicylate) silicon dianion (1
1) Bis(1,10-bisphenyldiorad)bis(tert-butoxy)silicon anion In the case of the above-mentioned exemplified compound groups B and C, only the anion is shown, but the counter ion is a proton. It may also be a cation of an alkali metal, an alkaline earth metal, ammonium, pyridinium, or a derivative thereof.

In the toner of the present invention, the silicon-containing complex compound is added to a known toner composition comprising a colorant and a binder resin. The amount added is based on 100 parts by weight of the toner composition.
It is added in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. In that case, the silicon-containing complex compound is
In addition to being dispersed or dissolved inside the toner, it may be selectively added only to the surface layer of the toner, or may be added and mixed outside the toner. In addition, when adding and mixing a silicon-containing complex compound into a toner, in addition to mechanically mixing it with a binder resin by a method such as melt mixing, emulsion mixing, or solution mixing, in the presence of a silicon-containing complex compound, the binder resin The monomers may be polymerized and the silicon-containing complex compound in the binder resin may be mixed or melted.

Binder resins that can be used in the present invention include conventionally known binder resins, such as styrene, vinyltoluene, styrene derivatives such as methylstyrene, chlorstyrene, and aminostyrene, and substituted products thereof, methyl methacrylate, Nistyl methacrylates such as ethyl methacrylate and butyl methacrylate; acrylic acid esters such as methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; and dienes such as acrylic acid, butadiene and isoprene; acrylonitrile; Vinyl ethers, maleic acid, maleic esters, maleic anhydride, vinyl monomers such as vinyl chloride, vinyl acetate, etc. alone or copolymers, olefinic polymers such as polyethylene and polypropylene, natural and synthetic waxes Polyester, polyamide, epoxy resin, polycarbonate, polyurethane, silicone resin, fluororesin, petroleum resin, etc. can be used alone or in combination.

Colorants used in the toner of the present invention include black dyes and pigments such as carbon black, oil black, and graphite;
, 1, Pigment Yellow 1, 3, 74, 97
, 98, etc., acetoacetate arylamide type monoazo yellow pigment (fast yellow type); C, I.

Pigment Yellow 12, I3, 14, and other acetoacetate arylamide disazo yellow pigments, C,1, Solvent Yellow 19, 77, 79, C11, Disperse Yellow 164, and other yellow dyes, C,1 , Pigment Red 48, Pigment Red 49:1, Pigment Red 53:1, Pigment Red 57
・Red or purple pigments of 1, 81, 122, 5 grade,
Red dyes such as C,1, Solvent Red 52, Solvent Red 58, and Solvent Red 8 - C1, Pigment Blue 15:3, etc., blue dyes and pigments such as copper phthalocyanine and its derivatives and modified products, C1 Pigment Green 7 , 36 (phthalocyanine green), colored or colorless sublimable dyes, and other dyes and pigments conventionally known for printing inks and other coloring applications can be used.

These dyes and pigments may be used alone or in combination of two or more. Of course, the color tone may be adjusted by mixing with an extender pigment or a white pigment. In addition, in order to improve the dispersibility in the binder resin,
The surface of the colorant may be treated with a surfactant, a coupling agent such as a silane coupling agent, or a polymer material, or a polymer dye or a polymer graft pigment may be used.

The concentration of the colorant in the toner depends on the specific gravity of the toner constituent materials such as the binder resin and colorant, the coloring power of the colorant, the particle size distribution of the toner particles, etc., and also depends on the amount of developed toner and the toner particle layer thickness. For example, in the case of a toner with an average particle size d50 of about 10 layers, if the layer thickness of the developed toner particles is controlled to approximately one or two layers, it is generally difficult to determine.
The content of the colorant is suitably about 2% by weight to 10% by weight. Naturally, if the average particle size of the toner is larger,
The colorant concentration is lower, and conversely, if the average particle size of the toner is small, the colorant concentration is adjusted higher.

The toner of the present invention exhibits sufficiently excellent negative chargeability by itself, but if necessary, it may contain a magnetic material such as ferrite, a conductivity regulator, tin oxide, silica, alumina, titanium oxide, zinc oxide, etc. Inorganic substances such as metal oxides, extender pigments, reinforcing fillers such as fibrous substances, antioxidants, mold release agents, etc. can be added.

Furthermore, it improves the powder fluidity and charging properties of the toner on the surface of the toner particles, prevents toner from filming on the surface of the photoconductor and carrier particles, and improves the cleaning performance of residual toner on the photoconductor. For this purpose, various external additives can be attached or fixed. These external additives include higher fatty acids such as stearic acid and derivatives such as their metal salts, esters, and amides, carbon black, tin oxide, graphite fluoride, silicon carbide, boron nitride, silica, alumina, and titanium dioxide. , inorganic powders such as zinc oxide, resin powders such as fluorine thread resins, acrylic resins, and silicone resins, polycyclic aromatic compounds, wax-like substances, and other conventionally known materials can be used.

As a method for producing the toner of the present invention, all conventionally known methods can be used, such as a kneading and pulverizing method, a spray drying method, and a direct polymerization method. The toner of the present invention has an average particle diameter d50 of I to 20 as measured by Coulter counter method.
It is desirable that the concentration, preferably d50, be adjusted to between 5 and 15 IMl.

All known developing methods can be applied as a method for converting electrical latent images and other electrical signals into visible images using the toner of the present invention, and in addition to the usual two-component developing method, microtoning method, etc. , it can also be applied to a -component development method without using a carrier.

(Example) The present invention will be explained below with reference to Examples. In addition, in the example “
"Parts" means "parts by weight" unless otherwise specified. Also, high temperature and high humidity is 28℃, 85% R11, low temperature and low humidity is 10℃, 15
%RH environment.

[Synthesis Example 1] Synthesis of Exemplary Compound (8) (bis(catecholate)phenylsilicon sodium salt) The following reaction was carried out under a nitrogen atmosphere.

a) 0.0475 mol trimethoxyphenylsilane/101 methanol b) 0.0475 mol sodium methoxide/
20+nl methanol c) 10.34g catechol/20ml methanol After stirring a) and b) at room temperature, C) was added dropwise at 25°C. The mixture was held at 45°C for 4 hours. Next, methanol was removed using a vacuum dryer, and the mixture was washed twice with ether. The mixture was left under vacuum at 100° C. for one day to obtain 13.2 g of Exemplified Compound (8). (Melting point: 220-230℃
) [Synthesis Example 2 Synthesis of Exemplary Compound (7) (Bis(2,8-naphthalenediol) silicon pyridinium salt) a) 0.1 mol 2,3-naphthalenediol/
Attach a reflux device to the container containing 3 ml pyridine b) and 0.05 mol phenyltotrimethoxysilane a), and add 90 ml of pyridine under nitrogen pressure.
℃ and mixed b) thereto and kept at the same temperature for 10 minutes. Thereafter, it was slowly cooled to room temperature. Post-treatment was performed in the same manner as in Synthesis Example 1 to obtain 19.5 g of Exemplary Compound (7). (
Melting point: 247°C) Example 1 Styrene acrylic resin (Sanyo Kasei, SBM-73) 95 parts Exemplary compound (3) [Compound of Synthesis Example 1] 2 parts Brilliant Carmine 6B pigment 3 parts A mixture of the above composition was mixed in a usual way. Manufactured by pulverization classification method, with an average particle size of 1
A 2μ magenta toner was obtained. This was mixed with a carrier in which 1100 tI ferrite was uniformly coated with 1% by weight of polymethyl methacrylate at a weight ratio of 3:100 to obtain a magenta developer.

When the obtained developer was put into a dry color copying machine FX-8800 manufactured by Fuji Xerox and a copying operation was performed, a clear magenta-colored copy image was obtained without skipping, image disturbance, or fog.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be extremely good.

Example 2 Styrene acrylic resin (Sanyo Kasei, SBM-73) 95 parts Exemplary compound (7) [Compound of Synthesis Example 2] 2 parts Copper phthalocyanine pigment 3 parts A mixture of the above composition,
A cyan toner having an average particle size of 12 mm was prepared by processing in exactly the same manner as in Example 1, and mixed with the same carrier as in Example 1 to obtain a cyan developer. Insert this into the Fuji Xerox dry color copier px-egoo,
When the copy operation was performed, a clear cyan-colored copy image was obtained with no image skipping, distortion, or fogging.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be an extremely good tool.

Example 3 Styrene acrylic resin (Sanyo Kasei, SBM-73) '95 parts Exemplary compound (10) 2 parts Bisazo yellow pigment 3 parts A mixture having the above composition was treated in exactly the same manner as in Example 1, and the average A yellow toner having a particle size of 1277 m was prepared and mixed with the same carrier as in Example 1 to obtain a yellow developer. When a copy operation was performed in the same manner as in Example 1,
A clear yellow copy image was obtained with no image skipping, turbulence, or fog.

Furthermore, when we used this developer to perform continuous, long-term, repeated copying operations of 10,000 copies in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial image quality, and it was found that the toner could be used as a full-color toner. It has been proven to be extremely effective.

Furthermore, when the toner and developer obtained in Examples 1.2 and 3 were simultaneously put into a copying machine (FX6800) and a copying operation was performed, a high-quality image showing extremely clear and wide color reproduction was obtained. A copy was obtained.

Example 4 Styrene acrylic resin (Sanyo Kasei, SBM-73) 95 parts Exemplary compound (10) 2 parts Quinacridone magenta pigment 3 parts A mixture having the above composition was treated in exactly the same manner as in Example 1 to determine the average particle size. 1
A 21IM magenta toner was prepared and mixed in the same manner as in Example 1 with the same carrier to obtain a magenta developer. When a copying operation was performed in the same manner as in Example 1, a clear magenta-colored copy image was obtained without image skipping, image disturbance, or fog.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven that it is an extremely good tool.

Example 5 Styrene acrylic resin (Sanyo Kasei, SBM-73) 95 parts Exemplary compound (9) 2 parts Phthalocyanine pigment 8 parts A mixture having the above composition was treated in exactly the same manner as in Example 1 to obtain an average particle size of 12 m+ A cyan toner was prepared and mixed with the same carrier as in Example 1 to obtain a cyan developer.

When a copying operation was carried out in the same manner as in Example 1, a clear cyan-colored copy image without image skipping, image disturbance, or fogging was obtained.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be an extremely good tool.

Example 6 Styrene acrylic resin (Sanyo Kasei, SBM-73) 95 parts Exemplary compound (10) 2 parts Fast Yellow FGL pigment 3 parts A mixture having the above composition was treated in exactly the same manner as in Example 1 to obtain an average particle size. A yellow toner having a diameter of 12 mm was prepared and mixed with the same carrier as in Example 1 to obtain a yellow developer. When a copying operation was carried out in the same manner as in Example 1, a clear yellow copy image without image skipping, image disturbance, or fogging was obtained.

Example 7 Low molecular weight polyester resin 95 parts (trade name: 5PARII K, manufactured by Kao ■) Exemplary compound (10
) 2 parts Rhodamine B lake pigment 3 parts A mixture of the above composition was treated in exactly the same manner as in Example 1 to prepare a magenta toner with an average particle size of 12, and mixed in the same manner as in Example 1 with the same carrier. A magenta developer was obtained. When a copying operation was carried out in the same manner as in Example 1, a clear magenta-colored copy image was obtained without skipping, image disturbance, or fogging.

Furthermore, when we used this developer to perform continuous, long-term, repeated copying operations of 10,000 copies in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial image quality, and it was found that the toner could be used as a full-color toner. It has been proven to be extremely good.

Example 8 Low molecular weight polyester resin 95 parts (trade name: 5PAR [rK, manufactured by Kao ■) Exemplary compound (5) 2
Copper phthalocyanine pigment 3 parts A mixture having the above composition was treated in exactly the same manner as in Example 1 to prepare a cyan toner having an average particle size of 1.2, and mixed in the same manner as in Example 1 with the same carrier. A cyan developer was obtained. When a copying operation was carried out in the same manner as in Example 1, a clear cyan-colored copy image without image skipping, image disturbance, or fogging was obtained.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be extremely good.

Example 9 Low molecular weight polyester resin 95 parts (trade name: 5PAI?nK, manufactured by Kao ■) Exemplary compound (3) 2
1 part disazo yellow pigment 3 parts The mixture having the above composition was treated in exactly the same manner as in Example 1 to prepare a yellow toner having an average particle size of I2ρ, and mixed in the same manner as in Example 1 with the same carrier to produce a yellow toner. A developer was obtained.

When copying was carried out in the same manner as in Example 1, a clear yellow copy image was obtained with no image scattering or fogging.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be extremely good.

Furthermore, when the toner and developer obtained in Examples 7.8 and 9 were simultaneously put into a copying machine (FX6800) and a copy operation was performed, high-quality copies were obtained that were very clear and had a wide color reproduction range. I got something.

Example 10 Low molecular weight polyester resin 95 parts (trade name: 5PARnK, manufactured by Kao ■) Exemplary compound (3) 2 parts Carbon black pigment 3 parts A mixture having the above composition was treated in exactly the same manner as in Example 1, A black toner having an average particle size of 12 uM was prepared and mixed with the same carrier as in Example 1 to obtain a black developer. When a copy operation was performed in the same manner as in Example 1,
A clear black copy image with no image skipping, turbulence, or fogging was obtained.

Furthermore, when we used this developer to repeatedly copy 100,000 sheets over a long period of time in environments of low temperature, low humidity, and high temperature and high humidity, the image quality and color reproduction were exactly the same as the initial version, and it was used as a full-color toner. It has been proven to be extremely good.

Furthermore, when the toner and developer obtained in Examples 7, 8, 9, and 10 were simultaneously put into a copying machine (FX6800) and a copy operation was performed, high image quality showing very clear and wide color reproduction range was obtained. A copy of was obtained.

Comparative Example 1 A magenta toner was prepared in the same manner as in Example 1 except that exemplified compound (3) was not used, and evaluated in the same manner as in Example 1. , and toner cracking was observed from the initial stage of operation, and it was determined that the toner was unsuitable as a toner.

Comparative Example 2 The same procedure as in Example 1 was carried out except that a chromium complex of monoazo dye (trade name Spironobrasoc TRH, commercially available as a charge control agent from Hodogaya Chemical Industry Co., Ltd.) was used instead of Exemplified Compound (3). A black toner was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. Although no image scattering, disturbance, or fogging was observed, the color reproduction was significantly inferior, and full color It was determined that the toner was unsuitable for use as a toner for commercial use.

Comparative Example 3 A magenta toner was prepared in the same manner as in Example 7, except that the exemplified compound (10) was not used, and evaluated in the same manner as in Example 7. As a result, image scattering, disturbance, and fogging occurred. It was determined that the image quality was so poor that it could not be used as a full-color toner.

Comparative Example 4 Example 7 except that an aluminum complex of aromatic salicylic acid (trade name Bontron E-88, commercially available as a charge control agent from Orient Chemical Industry Co., Ltd.) was used instead of Exemplified Compound (10). When a magenta toner was prepared in the same manner as in Example 7 and evaluated in the same manner as in Example 1, it was found that although there was a significant improvement in color reproduction, image scattering, disturbance, and fogging occurred. The image quality was so poor that it was judged that it could not be used as a full-color toner.

(Effects of the Invention) The silicon-containing complex compound of the present invention is a colorless negative charge control agent with excellent negative chargeability, and the toner of the present invention using the same has a chargeability of It has excellent environmental stability and charging stability during repeated use, exhibits excellent color reproducibility, and is suitable as a full-color toner.

Claims (1)

[Claims] (1) A monocyclic or polycyclic aromatic diol, a monocyclic or polycyclic aromatic hydroxycarboxylic acid, or a monocyclic aromatic diol containing a silicon atom as an essential component and capable of forming a chelate in an amount of 2 moles or more per mole of silicon. Alternatively, a toner for developing an electrostatic image, comprising a complex compound coordinated with a polycyclic aromatic dicarboxylic acid.